CN106986989B

CN106986989B - Preparation method of polyamide hollow nano-microspheres

Info

Publication number: CN106986989B
Application number: CN201710345514.4A
Authority: CN
Inventors: 丁晓莉; 华明明; 赵红永
Original assignee: Tianjin Polytechnic University
Current assignee: Tianjin Polytechnic University
Priority date: 2017-05-12
Filing date: 2017-05-12
Publication date: 2020-10-27
Anticipated expiration: 2037-05-12
Also published as: CN106986989A

Abstract

The invention relates to preparation of a nano material, in particular to a preparation method of a polyamide hollow nano microsphere, which can be carried out according to three schemes. The first scheme is as follows: dissolving water-soluble monomers such as m-phenylenediamine in water, mixing the water solution with a certain amount of oil phase solvent and an auxiliary agent to form a water-in-oil type microemulsion, dissolving a certain amount of oil-soluble monomers such as trimesoyl chloride in the microemulsion, reacting for a certain time, and removing the solvent to obtain the polyamide hollow nano-microspheres; scheme II: dissolving oil-soluble monomers such as trimesoyl chloride and the like in an oil phase solvent, mixing the solution with a certain amount of water and an auxiliary agent to form an oil-in-water microemulsion, dissolving a certain amount of water-soluble monomers such as m-phenylenediamine and the like in the microemulsion, reacting for a certain time, and removing the solvent to obtain the polyamide hollow nano-microspheres.

Description

Preparation method of polyamide hollow nano-microspheres

Technical Field

The invention relates to a nanotechnology, in particular to a preparation method of polyamide hollow nanospheres.

Background

In recent years, various nano materials with special structures and special appearances have attracted extensive attention, and one of them is a hollow nano microsphere material. The hollow nano-microsphere is formed by the evolution of a core/shell composite structure material, and the properties of the hollow nano-microsphere can be controllably adjusted by adjusting the structure, the size and the components of heterogeneous core/shell composite particles, so that the optical, thermal, electrical, magnetic and catalytic properties of the hollow nano-microsphere can be cut in a large range. The material with the structure has the characteristics of low density and high specific surface, and the hollow part of the material can contain a large amount of object molecules or large-sized objects, so that the material can generate peculiar properties based on a microscopic 'wrapping' effect, and the hollow nano microsphere material has important functions in a plurality of technical fields of medicine, biochemistry, chemical industry and the like.

The preparation of hollow microspheres is generally carried out in several ways: (1) removing the template, and preparing the hollow sphere. In the preparation process, the precipitation or reaction of the precursor on the surface of the core template is controlled to form a core/shell structure coated on the surface, the core template is removed by a heating or chemical reaction method, and the hollow sphere structure is obtained, wherein the size of the sphere is determined by the size of the template particles. (2) A microemulsion method is characterized in that a microemulsion drop is used as a template, a precursor of a target product is hydrolyzed on the surface of the microemulsion drop to generate corresponding hydroxide or hydrous oxide, then stable colloid particles are formed through polycondensation reaction and coated on the surface of the microemulsion drop to form a core-shell structure of emulsion/gel, the product is separated from the microemulsion through a method of adding water, acetone and other organic solvents, and then the surfactant and the organic solvents are removed through calcination to obtain a hollow sphere structure of the target product. The method can be used for preparing hollow spheres with the size from nanometer to micrometer and hollow spheres with mesoporous channels in the spherical shells. (3) The spray reaction method comprises the steps of preparing a target precursor into a solution by using water, ethanol or other solvents, atomizing the solution by using an atomizing device, enabling the atomized solution to form liquid drops through a nozzle, enabling the liquid drops to enter a reactor, enabling the solvent on the surfaces of the liquid drops to be rapidly evaporated, enabling solutes to be subjected to chemical reactions such as thermal decomposition or combustion, and depositing to form a hollow spherical shell, so that the structure of the hollow sphere is obtained. (4) In the ultrasonic method, ultrasonic cavitation bubbles generated by ultrasonic waves release huge energy when exploding, so that a local high-temperature high-pressure environment and micro-jet with strong impact force are generated, and a plurality of chemical reactions can be driven. (5) The template-interface reaction method limits chemical reaction on the surface of a nuclear template, and generates a hollow structure of a material through the chemical reaction. In the reaction process, the template is taken as a reactant to participate in the reaction, and the product is coated on the unreacted template as a shell. With the progress of the reaction, the amount of the core template is gradually reduced, the thickness of the shell layer is continuously increased, and finally, the reaction product forms a hollow microsphere structure. (7) The layer-by-layer self-assembly method includes adding colloid particles with negative (positive) charges as template into poly cation (anion) solution, separating from the solution by ultracentrifugation after saturation of adsorption, adding into poly anion (cation) solution, and repeating the steps to obtain multilayer film structure. After the assembly of the multilayer film on the particle template is completed, the core template is dissolved out, and finally the hollow sphere structure containing the nano particles, the polyelectrolyte and the like is obtained.

The preparation of polyamide microspheres is less reported in the literature, and the report of hollow type is more rare.

Disclosure of Invention

The invention aims to provide a simple method for preparing polyamide hollow nano microspheres. The method comprises two schemes.

The first scheme comprises the following steps:

1) dissolving a quantity of water-soluble amine monomer in water;

2) mixing the aqueous solution prepared in the step 1) in the scheme I with a certain amount of oil phase solvent and a certain amount of auxiliary agent to form water-in-oil type microemulsion;

3) dissolving a certain amount of oil-soluble acyl chloride monomer in the microemulsion prepared in the step 2) in the scheme I, carrying out interfacial polymerization on the water-soluble monomer and the oil-soluble monomer at an oil-water interface, evaporating to remove part of the solvent after reacting for a period of time, and drying in a vacuum oven to form the hollow nano microspheres.

The second scheme comprises the following steps:

1) dissolving a certain amount of oil-soluble acyl chloride monomer in an oil phase solvent;

2) mixing the oil phase solution prepared in the step 1) in the scheme II with a certain amount of water and a certain amount of auxiliary solvent to form oil-in-water microemulsion;

3) dissolving a certain amount of water-soluble amine monomer in the microemulsion prepared in the step 2) in the scheme II, carrying out interfacial polymerization on the water-soluble monomer and the oil-soluble monomer at an oil-water interface, evaporating to remove part of the solvent after reacting for a period of time, and drying in a vacuum oven to form the hollow nano microspheres.

The water-soluble amine monomer described in schemes one and two can be selected from one or a mixture of several of the following: phenylenediamine (e.g., m-phenylenediamine, p-phenylenediamine) and derivatives thereof, diethylenetriamine, triethylenetetramine, polyethyleneimine, methyl-m-phenylenediamine, ethylenediamine, hexamethylenediamine, octamethylenediamine, branched polyamidopolyamine, O' -bis (2-aminopropyl) polypropylene glycol-block-polyethylene glycol-block-polypropylene glycol.

The oil-soluble acyl chloride monomer described in schemes one and two can be selected from one or a mixture of more of the following: trimesoyl chloride, terephthaloyl chloride, isophthaloyl chloride, phthaloyl chloride, 1, 5-naphthalenedisulfonyl chloride, 1, 3, 6-trisulfonyl chloride, 5-oxoformyl chloride-isopeptide acyl chloride, 5-isocyanate-isopeptide acyl chloride, 1, 3, 5-cyclohexanetrioyl chloride, 3, 5, 5-biphenyltetracarboxylic acid chloride.

The water-in-oil microemulsion described in scheme one comprises the following systems: n-hexane/water/isopropanol, toluene/water/ethanol, oleic acid/water/n-propanol, furfural/water/methanol, furfural/water/ethanol, furfural/water/dimethylformamide, oleic acid/ammonia/gasoline/ethanol/water, oleic acid/ammonia/gasoline/n-propanol/water, oleic acid/ammonia/gasoline/n-butanol/water, oleic acid/ammonia/gasoline/n-pentanol/water, oleic acid/ammonia/gasoline/n-hexanol/hydro-oleic acid/ammonia/gasoline/n-heptanol/water.

The oil-in-water microemulsion described in scheme two comprises the following systems: toluene/water/ethanol, oleic acid/water/n-propanol, furfural/water/methanol, furfural/water/ethanol, furfural/water/dimethylformamide.

The invention has the following advantages: the hollow nano-microspheres are generated by reaction in a microemulsion system, and the rapid reaction between acyl chloride and amino is mainly utilized, so that the reaction is rapid; the adopted microemulsion system does not add a surfactant, the surfactant is removed without post-treatment, and the polyamide nano-microspheres can be obtained by directly removing the solvent. The method is simple, and has the advantages of few steps and less time consumption.

Drawings

FIG. 1 SEM photo of hollow nanospheres prepared from m-phenylenediamine and trimesoyl chloride in example 1

FIG. 2 TEM photograph of hollow nanospheres prepared with p-phenylenediamine and isophthaloyl dichloride in example 2

Detailed Description

Example 1

Preparing 10% m-phenylenediamine aqueous solution, and preparing the aqueous solution, n-hexane and isopropanol into microemulsion according to the mass ratio of 0.3: 0.25: 0.45; dissolving a certain amount of oil-soluble phase monomer (10% of the mass of the normal hexane in the microemulsion) in the microemulsion, reacting for 5min, evaporating part of the solvent, and then putting the microemulsion into a vacuum oven to dry and remove water and residual isopropanol and normal hexane. The particle size is shown in table 1.

TABLE 1

Example 2

Preparing 25% of methyl m-phenylenediamine aqueous solution, and preparing microemulsion from the aqueous solution, toluene and ethanol according to the mass ratio of 8.7: 55.7: 35.6; dissolving a certain amount of oil-soluble monomer (25% of the mass of toluene in the microemulsion) in the microemulsion, reacting for 5min, evaporating part of the solvent, and drying in a vacuum oven to remove water and residual isopropanol and n-hexane. The particle size is shown in table 2.

TABLE 2

Oil phase monomer	Outer diameter (nm)	Inner diameter (nm)
			Trimesoyl chloride	56	35
Terephthaloyl chloride	78	43
			Isophthaloyl dichloride	76	45
Phthaloyl chloride	87	41
			1, 5-naphthalenedisulphonyl chloride	88	47
1, 3, 6-trisulfonyl chlorides	84	60
			5-Oxocarboxyl chloride-isopeptide acid chloride	59	38
5-isocyanate-isopeptide acid chloride	71	41
			1, 3, 5-cyclohexanetricarboxylic acid chloride	67	27
3, 3, 5, 5-biphenyltetracarboxylic acid chloride	46	25

Example 3

Preparing a toluene solution of isophthaloyl dichloride (the mass content of acyl chloride is 15%), and preparing a microemulsion from oleic acid, water and isopropanol according to the mass ratio of 75: 10: 15; dissolving a certain amount of water phase monomer in the microemulsion, reacting for 3min, removing part of solvent by evaporation, and drying in a vacuum oven to remove water and residual ethanol and toluene. The particle size is shown in table 2.

TABLE 3

The above two examples do not indicate a limited scope of application of the patent. Any person skilled in the art can easily apply the teachings of the patent to any other possible system, such as piperazine and its derivatives, as water-soluble monomers, and other surfactant-free microemulsion systems.

Claims

1. A preparation method of polyamide hollow nano-microspheres is characterized by comprising the following steps: preparing 10% m-phenylenediamine aqueous solution, and preparing the aqueous solution, n-hexane and isopropanol into microemulsion according to the mass ratio of 0.3: 0.25: 0.45; dissolving an oil-soluble phase monomer which accounts for 10 percent of the mass of the normal hexane in the microemulsion into the microemulsion, evaporating partial solvent after reacting for 5min, and then putting the microemulsion into a vacuum oven to dry and remove water and residual isopropanol and normal hexane;

when the oil phase monomer is terephthaloyl chloride, the outer diameter of the product is 68nm, and the inner diameter is 40 nm;

when the oil phase monomer is isophthaloyl dichloride, the outer diameter of the product is 76nm, and the inner diameter of the product is 35 nm;

when the oil phase monomer is phthaloyl chloride, the outer diameter of the product is 57nm, and the inner diameter of the product is 29 nm;

when the oil phase monomer is 1, 5-naphthalene di-xanthoyl chloride, the outer diameter of the product is 48nm, and the inner diameter of the product is 17 nm;

when the oil phase monomer is 1, 3, 6-trisulfonyl chloride, the outer diameter of the product is 54nm, and the inner diameter of the product is 20 nm;

when the oil phase monomer is 5-oxoformyl chloride-isopeptide acyl chloride, the outer diameter of the product is 49nm, and the inner diameter of the product is 18 nm;

when the oil phase monomer is 5-isocyanate-isopeptide acyl chloride, the outer diameter of the product is 71nm, and the inner diameter is 40 nm;

when the oil phase monomer is 1, 3, 5-cyclohexane trimethyl acyl chloride, the outer diameter of the product is 57nm, and the inner diameter of the product is 37 nm;

when the oil phase monomer is 3, 3, 5, 5-biphenyl tetracarboxyl chloride, the outer diameter of the product is 56nm, and the inner diameter is 23 nm.